Resinous material



Patented Nov. 5, 1940 PATENT OFFICE RESINOUS MATERIAL Alexander N.

Woodbury,

Sachanen and Pharez G. Waldo, N. J., assignors to Socony-Vacuum corporation of New York Oil Company, Incorporated, New York, N. Y., a

No Drawing. Application January 12, 1938, Serial No. 184,596

2 Claims.

This invention relates to the production of materials of a resinous nature. In particular the invention is concerned with the production of oil soluble resins from petroleum products.

Heretofore formolite resinous compositions have been produced by the action of formaldehyde on petroleum distillates and crude oils in .the presence of sulphuric acid. Thesecondensation products produced in the past, the so-called formolites, are, however, oil insoluble resins, lacking the property of being easily molded and form brittle resins.

It is an object of this invention to provide a method for producing resinous materials from solvent tars. A more specific object of the invention is to produce resinous materials from products, our invention is based upon the discovery that oil soluble resins may be produced in substantial amounts by treating solvent tars under proper conditions with formaldehyde or suitable derivatives thereof. The resinous reaction product obtained contains in' addition to oil soluble resins some 'oil insoluble formolites and unreacted oil. These three components of the resinous product are usually present in approximately equal precentages but may be easily sep-'- arated by means of solvent extraction and distillation.

Solvent tar is the well known rejected product obtained from the solvent refining of lubricant oils. .In solvent refining a lubricating oil, a lubricating fraction of petroleum is contacted with a solvent capable of exerting selective solvent properties upon the various constituents thereof for the purpose of separating the raw stock into two fractions. The rafiinate or refined stock is a product of more highly paraflinic nature, more stable, of higher viscosity index and a better lubricant. The solvent tar or discarded'stock is more highly naphthenio and aromatic and of much lower viscosity index. As is well known, solvent tars vary in the amount of aromatic constltuents which they contain. The aromaticity of the tars varies according to the crude oil from which the petroleum fraction is derived to make the solvent tar; Thus, a solvent tar produced by refining a Coastal or a Mid-Continent oil is usually more highly aromatic than a solvent tar produced by refining a Pennsylvania oil.

In the practice of our invention we may employ any solvent tar which contains aromatic constituents; however, better results are obtained by use of solvent tars containing relatively high percentages of aromatic constituents. Accordingly, for our purpose, we prefer to use solvent tars of the class which contain at least of aromatic constituents (as measured by absorption with strong sulphuric acid), and especially suitable are the solvent tars containing at least of aromatic constituents, such as a furfural solvent tar obtained from the treatment of distillates from Mirando crude. Other solvent tars which may be mentioned merely by way of example as suitable tars for the practice of our invention are the solvent tars obtained in the refining of distillates from. East Texas crude and Rodessa crude. It is to be clearly understood, however, that the invention is not limited to the use of the specific tars mentioned since solvent tars in general containing aromatic compounds may be used.

In place of formaldehyde various derivatives thereof may be employed as the resinifying agent, such as paraformaldehyde and hexamethylenetetramine. In view of the fact that all of these compounds have formaldehyde as a basis, for conveniencetheywill be referred to hereinafter in the specification and claims as formaldehyde resinifying agents.

In accordance with our invention, a suitable solvent tar is mixed with a formaldehyde resini able solvent such as-petroleum ether or other suitable petroleum fraction, benzene, etc.

After the extraction, the solvent extract which contains the oil soluble resins and unreacted oil, is

that is, about 30 to of the amount of tar for each product.

While it is preferred to use sulphuric acid as the catalyst, the invention is not limited thereto, I

but mineral acids in general having a similar strength, such as hydrochloric, etc. may be used to give the desired acidity. After the completion of the reaction, water or acetic acid may be added to dilute the reaction mixture so as to aid in separation and removal of the sulphuric acid.

The oil soluble resins produced by our process are solid at normal temperature and on heating they are gradually liquifled. Their color is dark red with a green fluorescence. Further, these resins are completely miscible with all oil products and when dissolved in oils they increase the viscosity of the oil. It has been found that these oil soluble resins also can be used for varnishes and other coatings and can be admixed with other resins to increase the plasticity of the resultant product.

While the oil insoluble resins may be used as such for certain purposes, they also can be admixed with other resins and used in various arts, for example molding.

The distillate oil obtained from our process can be used as a highly refined lubricating oil where a high viscosity index is not necessary. The viscosity index of these distillates usually does not exceed 0-20.

The invention will be further illustrated by the following examples. However, it is to be understoodthat the invention is in no way limited thereto.

Example 1.One part of solvent tar (containing more than about 75 to 80% aromatic hydrocarbons) is mixed with approximately 10% by weight of paraformaldehyde, and while stirred continuously reacted for a period of about one hour in the presence of one part by volume of sulphuric acid (92%). Instead of paraformaldehyde, aqueous formaldehyde (30%) may be used in the amount of one volume with respect to the solvent tar. The resinous material produced is separated from the aqueous solution of sulphuric acid and excess formaldehyde, washed,

dried and then extracted with petroleum ether.

The petroleum ether extract containing the oil soluble resins and unreacted oil is then evaporated to remove the ether and distilled in vacuo to remove the oil. The total yield of raw formolites (oil insoluble formolites, oil soluble resins and unreacted oil) is about 100% based on the amount of tar used or slightly more. The yield of 011 soluble resins is about 35% of the amount of solvent tar and the yield of oil insoluble resin is similar.

Thai mixture is stirred for one-half hour then diluted with water; -filtered, washed, dried and extracted with petroleum ether. Petroleum ether extract is evaporated to remove petroleum ether, and the residue is'distilled in vacuo. The 15 yields of the products are as follows:

The mixture is stirred for one half hour. The subsequent operations are the same as in Example 2. The yields of the products are as follows:

Formolites gr 15 Oil soluble resins .gr 13 Distillate oil gr 22 Since certain changes may be made in the Formolites gr 15 Oil soluble resins gr 2'! Distillate oil gr 10 20 Example 3 Furfural tar gr 50 Paraformaldehyde gr 5 Sulphuric acid (80%) cc 50 25 invention without departing from the scope 35 thereof, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

We claim:

I 1'. The method of preparing an oil soluble resinous material which comprises reacting a petroleum solvent tar containing at least 65% of aromatic constituents with approximately 10% by weight of a formaldehyde resinifying agent in the presence of a strong mineral acid 2. The oil soluble resin product prepared in u accordance with the method of claim 1.

ALEXANDER N. SACHANEN. PHAREZ G. WALDO. 

